亚临界和超临界二氧化碳-甲醇混合气相及液相区中甲醇核磁弛豫速率比较研究

doi:10.3866/PKU.WHXB201608122

Abstract

Abstract:

¹H NMR longitudinal relaxation times (T_{1, exp} of the hydroxyl and methyl group) of methanol in supercritical and subcritical gas-like and liquid-like CO₂+methanol mixtures were obtained as a function of pressure up to 25 MPa and at 293.15 and 308.15 K, respectively. This study was designed to investigate the mechanism of the spin-lattice relaxation (SLR) time T1 in different phase regions of CO₂+methanol as homogenous gas-like, and liquid-like mixtures, and the influence of pressure, temperature, and composition on the relaxation rate was examined. Moreover, the density dependent isotherms of the SLR rates 1/T_{1, exp} were comparatively studied between gas-like and liquid-like binary mixtures. There exists an obvious phase dependent SLR mechanism within the temperature and pressure range carried out herein, that is, the SLR process is dominated by the dipole-dipole (DD) interaction mechanism for both liquid-like mixture and methanol, whereas by the spin-rotation (SR) mechanism for gas-like mixture. Measurement of nuclear magnetic relaxation times can offer micro-dynamic and micro-structural information and are very useful for the study of fluids of strongly interacting molecules. Mutual influence of electric dipoles as well as hydrogen bonds helps determine the structure of the fluid and its molecular dynamics. The present work increases our knowledge of molecular dynamics of alcohols in sub-and supercritical CO₂.

Key words: CO₂-methanol mixture, Dipole-dipole interaction mechanism, Subcritical and supercritical fluid, Spin-lattice relaxation rate, Spin-rotation mechanism

Xiao-Meng CHENG,Yu LI,Zong CHEN,Hong-Ping LI,Xiao-Fang ZHENG. A Comparative Study on theNMR Relaxation of Methanol in Sub-and Super-Critical Mixtures of CO₂ and Methanol[J]. Acta Phys. -Chim. Sin. 2016, 32(11), 2671-2677. doi: 10.3866/PKU.WHXB201608122

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A Comparative Study on theNMR Relaxation of Methanol in Sub-and Super-Critical Mixtures of CO₂ and Methanol

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A Comparative Study on theNMR Relaxation of Methanol in Sub-and Super-Critical Mixtures of CO₂ and Methanol